ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Ab initio and model calculations on linear clusters of acetylene molecules have been carried out to identify the effect of weak intermolecular interaction on the intrinsic dipole polarizability (-) and the second hyperpolarizability (γ) and, in particular, to determine the three-body and higher-order effects. Ab initio and model calculations on a linear dimer show clearly that the evolution of properties from the separated limit is largely a consequence of the mutual polarization as the monomers begin to interact. This reveals that intermolecular quantum features are not significant. Furthermore, higher-order response properties play a negligible role in the evolution of lower-order cluster properties. For instance, the hyperpolarizability γ of the monomer is relatively unimportant in the evolution of α of the dimer; the change in α due to dimer formation is dictated largely by the mutual polarization via the intrinsic α′s of the monomer. With this determination, an electrical interaction model can be used to explore α and γ of long acetylene chains, and this serves as a guide to the vibronic coupling effects on hyperpolarizabilities of longchain species. We find, in particular, that the hyperpolarizability of the subunits of long acetylene chains are dramatically enhanced by intermolecular electrical interaction.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560430112
